US3963737A - 1,3-Dihydrocarbyl-pyrazole compounds as stabilizers for organic materials - Google Patents

1,3-Dihydrocarbyl-pyrazole compounds as stabilizers for organic materials Download PDF

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Publication number
US3963737A
US3963737A US05/592,369 US59236975A US3963737A US 3963737 A US3963737 A US 3963737A US 59236975 A US59236975 A US 59236975A US 3963737 A US3963737 A US 3963737A
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alkyl
phenyl
unsubstituted
substituted
formula
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US05/592,369
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English (en)
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Lajos Avar
Kurt Hofer
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Sandoz AG
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Sandoz AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring

Definitions

  • the present invention relates to derivatives of pyrazole compounds which are useful as stabilizers of organic materials against the adverse effects of ultraviolet light.
  • the present invention provides 1,3-dihydrocarbyl-pyrazole compounds, having a 5-hydroxyl group in free or nickel salt form, characterized by a ketoxyimino group bound directly to the 4-position of the pyrazole ring through the ketoxyimino functional carbon atom.
  • ketoxyimino group is meant a group of the formula ##EQU1## the carbon atom *C being the ketoxyimino functional carbon atom.
  • a preferred class of pyrazole compounds from the above class of such compounds are those of formula I, ##SPC1##
  • R 1 is C 5 -C 17 alkyl; phenyl-C 1 -C 4 alkyl, of which the phenyl radical is unsubstituted or substituted by up to 4 substituents selected from 1 or 2 hydroxyl and 1 or 2 C 1 -C 6 alkyl radicals; phenyl, unsubstituted or substituted by up to 3 substituents selected from 1 to 3 halogen atoms, a hydroxyl radical 1 or 2 C 1 -C 8 alkyl radicals, 1 or 2 C 1 -C 8 alkoxy radicals and a phenyl radical; or 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-benzothienyl or 3-benzothienyl, each of which heterocyclic radicals is unsubstituted or substituted by 1 or 2 halogen atoms or by a C 1 -C 4 alkyl radical,
  • R 2 and R 3 independently, is C 1 -C 8 alkyl or phenyl, the latter unsubstituted or substituted by up to 4 substituents selected from 1 or 2 halogen atoms and 1 or 2 C 1 -C 4 alkyl radicals,
  • M is hydrogen or an equivalent of nickel.
  • any alkyl radical may be straight or branched chain when containing 3 or more carbom atoms, and may be primary or secondary. Any such radical containing 4 or more carbon atoms may additionally be tertiary.
  • Halogen means fluorine, chlorine or bromine, of which chlorine is prefered.
  • R 1 is alkyl, this preferably contains 6 to 17 carbon atoms, more preferably 8 to 15 carbon atoms, and most preferably 9, 11 or 15 carbon atoms.
  • R 1 is an optionally substituted phenyl radical, this is preferably unsubstituted. However, when substituted, it preferably bears up to 3 substituents selected from a chlorine atom, a hydroxyl radical in the para position, 1 or 2 C 1 -C 4 alkyl racicals and 1 or 2 C 1 -C 4 alkoxy radicals, more preferably bears a single C 1 -C 4 alkyl substituent, and most preferably bears a tert.-butyl radical.
  • R 1 is alkyl or optionally substituted phenyl, more preferably alkyl.
  • R 2 or R 3 is alkyl, this preferably contains 1 to 4 carbon atoms, and most preferably is methyl.
  • R 2 or R 3 is an optionally substituted phenyl radical, this is preferably unsubstituted. However, when substituted, it preferably bears 1 or 2 C 1 -C 4 alkyl radicals.
  • R 2 preferably is alkyl or unsubstituted phenyl, more preferably unsubstituted phenyl
  • R 3 preferably is alkyl or unsubstituted phenyl, more preferably alkyl, particularly methyl.
  • M is preferably an equivalent of nickel.
  • R 1 ' is C 6 -C 17 alkyl or phenyl, unsubstituted or substituted by up to 3 substituents selected from a chlorine atom, a p-hydroxyl radical, 1 or 2 C 1 -C 4 alkyl radicals and 1 or 2 C 1 -C 4 alkoxy radicals,
  • each of R 2 ' and R 3 ' is C 1 -C 4 alkyl or phenyl, unsubstituted or substituted by 1 or 2 C 1 -C 4 alkyl radicals.
  • a preferred class of compounds of formula Ia is constituted by compounds of formula Ib, ##SPC3##
  • R 1 " is C 8 -C 15 alkyl or phenyl, unsubstituted or substituted by a C 1 -C 4 alkyl radical
  • R 2 " and R 3 " independently, is methyl or unsubstituted phenyl.
  • a preferred class of compounds of formula Ib is constituted by compounds of formula Ic. ##SPC4##
  • R 1 " is C 8 -C 15 alkyl or phenyl, unsubstituted or substituted by a C 1 -C 4 alkyl radical
  • R 2 '" is unsubstituted phenyl
  • R 3 '" is methyl
  • the invention further provides a process for the production of a pyrazole compound of the invention, as described above, which comprises reacting the corresponding pyrazole compound, wherein the 4-position is occupied by a keto group directly bound to that position by the carbonyl carbon atom, with hydroxylamine in free base or acid addition salt form, and when required, converting the free 5-hydroxyl group into the nickel salt form.
  • An example of the above process of the invention is a process for the production of a compound of formula I, as defined above, which comprises reacting a compound of formula II, ##SPC5##
  • R 1 , R 2 and R 3 are as defined above, with hydroxylamine in free base of acid addition salt form, and, when required, converting the free 5-hydroxyl group into the nickel salt form.
  • suitable salts of hydroxylamine which may be used instead of the free base form include the hydrochloride, hydrobromide, acetate, sulphate and tartrate.
  • reaction conditions use for the process may be those conventionally employed for converting a carbonyl group to its oxime derivative, and, in the case where the free 5-hydroxyl group is to be converted into the nickel salt form, for effecting such a conversion.
  • the compounds of formula II used as the starting materials in the particular example of the process of the invention given above may be produced in conventional manner from known starting materials or from starting materials produced by analogous processes to those for producing the known starting materials.
  • the present invention further provides a method of stabilizing an organic material against the degradative effects of ultraviolet light comprising "treating" the organic material with a pyrazole compound of the invention, as described above.
  • treating is meant either incorporating into the body of the organic material or surface coating the organic material, in a manner known per se.
  • Suitable organic materials which benefit from the method of the present invention include such natural substances as rubber, cellulose, wool and silk, and plastics materials, in particular polyolefins, e.g., polyethylene and polypropylene, polyesters, polyvinyl chloride, polymethyl methacrylates, polypropylene oxide, polyphenylene oxides, polyurethanes, polystyrene, cellulose acetobutyrate, polyamides, e.g., nylon, polyacrylonitrile, polycarbonate, copolymers of the aforementioned polymers, and ABS-terpolymers.
  • polyolefins e.g., polyethylene and polypropylene
  • polyesters polyvinyl chloride, polymethyl methacrylates, polypropylene oxide, polyphenylene oxides, polyurethanes, polystyrene, cellulose acetobutyrate, polyamides, e.g., nylon, polyacrylonitrile, polycarbonate, copolymers of the aforementioned
  • the pyrazole compounds of the present invention are used for stabilizing polyethylene, polypropylene, polyesters, in particular polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyamide, polyurethanes, cellulose acetobutyrate, polystyrene, polyacrylonitrile, copolymers of styrene and acrylonitrile and of styrene and butadiene, ABS-terpolymers and terpolymers of acrylic ester, styrene and acrylonitrile.
  • the pyrazole compound is intimately mixed with the organic material to be treated, e.g., a plastics material such as polypropylene, preferably in granular form, in a kneader or other suitable mixing device, after which the material is extruded.
  • a plastics material such as polypropylene
  • the pyrazole compound is mixed with the appropriate monomer(s) and/or prepolymer before polymerization of copolymerization is effected.
  • the product After the polymerization or copolymerization the product has the compound distributed therethrough, and it may thereafter be extruded, moulded or otherwise formed into final shape.
  • the organic materials may also be treated with other additives besides the pyrazole compounds of the invention to improve their properties, e.g., other stabilizers or co-stabilizers, e.g., against the degradative effects of oxygen, heat and/or ultraviolet light.
  • other additives besides the pyrazole compounds of the invention e.g., other stabilizers or co-stabilizers, e.g., against the degradative effects of oxygen, heat and/or ultraviolet light.
  • the amount of stabilizing pyrazole compound employed in the method of the present invention will natuarally depend on several factors, including the mode of application, the particular compound employed and the nature of the organic material to be treated. However, satisfactory results are generally obtained when the amount of compound employed is in the range 0.01 to 5%, preferably 0.05 to 1%, of the weight of the organic material to be treated.
  • the present invention further provides an organic material whenever treated according to the method of the present invention.
  • Stabilized organic materials according to the present invention may exist in solid form, e.g., foam plastics, sheets, rods, coatings, plates, foils, films, strips, apes, loops, filaments, fibres, granules, powders and other working forms, or in liquid form, e.g., solutions, emulsions and dispersions.
  • the present invention is illustrated by the following Examples, in which the parts and percentages are by weight.
  • the indicated structures of the compounds are determined by microanalysis and infra-red spectroscopy.
  • Example 1 The compound of Example 1 is incorporated into 200 times its weight of non-stabilized polypropylene at 180°C in a roller mill, and the mixture is pressed into sheets of 0.3 mm thickness. These sheets are tested for their resistance agains u.v. light by the De La Rue method of the climate test. The test is carried out at 40°C, at 75% relative humidity and with strong ventilation using 16 Philips sunlamps and 16 Philips blacklamps, and satisfactory results are obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
US05/592,369 1974-07-09 1975-07-02 1,3-Dihydrocarbyl-pyrazole compounds as stabilizers for organic materials Expired - Lifetime US3963737A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH941874A CH581118A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-07-09 1974-07-09
CH9418/74 1974-07-09

Publications (1)

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US3963737A true US3963737A (en) 1976-06-15

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US (1) US3963737A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE831097R (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CH (1) CH581118A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2529052A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES439242A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2277828A2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1512044A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT1050694B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL7507990A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4146540A (en) * 1973-03-09 1979-03-27 Sandoz Ltd. Pyrazole compounds as stabilizers for organic materials
US6605658B1 (en) * 1999-11-23 2003-08-12 Great Lakes Chemical (Europe) Gmbh Stabilizing mixtures for organic polymers comprising a pyrazolone, an organic phosphite or phosphonite and a hindered phenol
US20040244643A1 (en) * 2003-06-05 2004-12-09 Voeght Frank De UV-absorbing ink composition for ink-jet printing

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5610305A (en) * 1995-11-22 1997-03-11 Uv Stab Ltd. Pyrazole-and piperidine-containing compounds and their metal complexes as light stabilizers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256291A (en) * 1965-03-08 1966-06-14 Du Pont Neutral and ionic chelates of 1-pyrazoledithiocarboxylic acids with divalent metals of atomic number 24-30
US3265705A (en) * 1965-06-09 1966-08-09 Du Pont Metal complexes of pyrazole-haloketones and preparation thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256291A (en) * 1965-03-08 1966-06-14 Du Pont Neutral and ionic chelates of 1-pyrazoledithiocarboxylic acids with divalent metals of atomic number 24-30
US3265705A (en) * 1965-06-09 1966-08-09 Du Pont Metal complexes of pyrazole-haloketones and preparation thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4146540A (en) * 1973-03-09 1979-03-27 Sandoz Ltd. Pyrazole compounds as stabilizers for organic materials
US6605658B1 (en) * 1999-11-23 2003-08-12 Great Lakes Chemical (Europe) Gmbh Stabilizing mixtures for organic polymers comprising a pyrazolone, an organic phosphite or phosphonite and a hindered phenol
US20040244643A1 (en) * 2003-06-05 2004-12-09 Voeght Frank De UV-absorbing ink composition for ink-jet printing
US7141104B2 (en) * 2003-06-05 2006-11-28 Agfa-Gevaert UV-absorbing ink composition for ink-jet printing

Also Published As

Publication number Publication date
NL7507990A (nl) 1976-01-13
CH581118A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1976-10-29
GB1512044A (en) 1978-05-24
DE2529052A1 (de) 1976-01-29
ES439242A1 (es) 1977-06-16
IT1050694B (it) 1981-03-20
FR2277828A2 (fr) 1976-02-06
FR2277828B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1979-08-10
BE831097R (fr) 1976-01-07

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